Metal-organic coordination architectures of condensed heterocyclic based 1,2,4-triazole: Syntheses, structures and emission properties

Article abstract of DOI:10.1016/j.poly.2012.05.028

In efforts to explore the effects of metal ions, ligand structures, counteranions on the structures and properties of metal-organic complexes, seven d¹⁰ metals (Zn and Cd) and transition metals (Cu and Co) coordination compounds with condensed

Full text of DOI:10.1016/j.poly.2012.05.028

Polyhedron 42 (2012) 216–226
Contents lists available at SciVerse ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
Metal–organic coordination architectures of condensed heterocyclic based
1,2,4-triazole: Syntheses, structures and emission properties
a
b
a
a
a
Duo-Zhi Wang a, , Qin Zhang , Jian-Bin Zhang , Yuan-Gao Wu , Ling-Hua Cao , Peng-Yuan Ma
⇑
a Xinjiang Laboratory of Advanced Functional Materials, Chemistry and Chemical Engineering School of Xinjiang University, Urumqi 830046, PR China
b Physics and Chemistry Test Center of Xinjiang University, Urumqi 830046, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
In efforts to explore the effects of metal ions, ligand structures, counteranions on the structures and
properties of metal-organic complexes, seven d10 metals (Zn and Cd) and transition metals (Cu and Co)
coordination compounds with condensed heterocyclic based 1,2,4-triazole 4,7-diphenyl-1,2,4-triazol-
o[3,4-b]-1,3,4-thiadiazole (L1), 4-phenyl-7-(pyridine-3-yl)-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazole (L2),
4-phenyl-7-(pyridine-4-yl)-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazole (L3), and 4-(pyridine-3-yl)-7-(pyri-
dine-4-yl)-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazole (L4), Zn(L1)2Cl2 (1), Co(L1)2Cl2 (2), {[Cd(L2)2(H2O)2]ꢀ
(ClO4)2} (3), Cd(L2)2(NO3)2(H2O)2 (4), {[Cu(L3)2(NO3)2]ꢀ(CH2Cl2)} (5), {[Cu(L3)2(OH)(MeOH)]ꢀ(MeOH)2ꢀ
Received 12 April 2012
Accepted 17 May 2012
Available online 9 June 2012
Keywords:
Triazole ligands
Metal complexes
Crystal structure
Emission properties
1
1
BF4} (6) and [Cd(L4)2(NO3)2] (7) were synthesized and structurally characterized by elemental analy-
1
1
ses, IR spectroscopy and single-crystal X-ray diffraction. Complexes 1, 2 and 4 have a mononuclear struc-
ture, 1 and 2 have similar structure, 3 and 6 have a neutral rhombohedral grid with a (4, 4) topology, the
coordination network of 3 further assembled into a three-dimensional framework by O–Hꢀ ꢀ ꢀO hydrogen-
bonding interactions,
5 reveals a coordination chain structures consisting of a neutral chain
{[Cu(L3)2(NO3)2]ꢀ(CH2Cl2)} with the CuII centers, and 7 has a coordination chain. Obviously, the struc-
1
tural differences among them are attributable to the difference of metal ions, counter-anions, the locality
and amount of coordination atoms in ligands framework. All the complexes are air stable at room tem-
perature. Furthermore, the fluorescent properties of complexes 1, 3, 4, 7 and corresponding ligands have
been investigated and discussed.
Ó 2012 Elsevier Ltd. All rights reserved.
1. Introduction
counter-ions, the reaction solvent and temperature, pH value etc.
A careful choice or design of organic ligands coupled with suitable
Metal-organic frameworks (MOFs) have received much interest
due to their various potential applications such as optical nonlin-
earity, luminescence, magnetism, conductivity, catalytic activity,
selective adsorption/separation, and their topological features [1].
In recent years, polydentate aromatic nitrogen heterocyclic ligands
with five-membered rings (azoles) have been well used in the con-
struction of supramolecular structures [2]. Among polyazoles, imi-
dazoles and triazoles ligands have been extensively used to
construct various coordination networks with diverse topologies
and interesting properties [3]. The structure and properties of
metal complexes depend on the metal ion and the donor atoms,
as well as the structure of the ligand and the metal–ligand interac-
tions [4]. However, the construction of the coordination polymers
with desired topologies and specific properties still remains a
far-reaching challenge since there are so many factors influencing
the formation and structure of the complexes such as the geomet-
ric requirements of metal ions, the character of the ligands,
metal ions may lead to new complexes with specific structures and
properties [5–9].
Great efforts have been focused on ligands based on azole het-
erocycles, which have both good coordination ability and diverse
coordination modes [10]. As the simple small molecular ligands,
1,2,4-triazole and its derivatives are very interesting not only be-
cause they can be used as spin crossover materials which has the
potential application in information storage but also they can form
a variety of novel structural motifs [11]. Until now, 1,2,4-triazole,
especially its derivatives, gains more interest as ligands to bridge
different metal ions to form functional coordination polymers
because of their potential bridging fashions [3c,12]. For example,
some complexes containing 1,4-bis(triazol-1-ylmethyl)benzene
with the third order NLO (nonlinear optics) properties and the
fluorescence properties have been documented [13]. Previously,
we reported a series of bis-triazole ligands, 9,10-bis(triazol-1-
ylmethyl)anthracene with d10 metal coordination polymers with
better luminescence properties [14]; and some transition metal-
organic coordination complexes with 1,4-bis(1,2,4-triazol-1-
ylmethyl)naphthalene/4,40-bis(1,2,4-triazol-1-ylmethyl)biphenyl
⇑
Corresponding author.
E-mail address: wangdz@xju.edu.cn (D.-Z. Wang).
0277-5387/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.poly.2012.05.028

D.-Z. Wang et al. / Polyhedron 42 (2012) 216–226
217
have been investigated [8b]. However, there are still only rare re-
benzoic acid / POCl
3
1
L
ports of ligands based on condensed heterocyclic based 1,2,4-tria-
zole as building blocks for the construction of coordination
complexes.
N
N
nicotinic acid / POCl
3
R
2
L
N
SH
In this work, four ligands of condensed heterocyclic based 1,2,4-
triazole: 4,7-diphenyl-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazole (L1),
4-phenyl-7-(pyridine-3-yl)-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazole
(L2), 4-phenyl-7-(pyridine-4-yl)-1,2,4-triazolo[3,4-b]-1,3,4-thiadi-
azole (L3), and 4-(pyridine-3-yl)-7-(pyridine-4-yl)-1,2,4-triazol-
o[3,4-b]-1,3,4-thiadiazole (L4), (Chart 1), have been designed and
synthesized. The reactions of these ligands with the corresponding
metal salts lead to the formation of seven new metal–organic com-
plexes with 0-D, 1-D and 2-D network structures. Herein, we re-
port the syntheses, crystal structures and emission properties of
these complexes. The influences of the locality and amount of coor-
dination atoms in the same ligands’ framework and counteranions
on the resultant structures of their metal complexes are briefly
discussed. In addition, the emission properties of part of these
complexes have also been investigated in the solid state at room
temperature.
NH
(a)
isonicotinic acid / POCl
3
3
4
2
L , L
N
1
2
3
4
L ,L ,L : R=
L : R=
Chart 2.
2.2.2. 4-phenyl-7-(pyridine-3-yl)-1,2,4-triazolo[3,4-b]-1,3,4-
thiadiazole(L2)
Ligand L2 were obtained by the similar method described for L1.
Yield: ꢂ60%. m.p. 239–240 °C. 1H NMR (CDCl3): d: 9.21(d, 1H, J = 2
Hz, pyridine-2), 8.86(dd, 1H, J = 1.6, 5.2 Hz, phenyl-4), 8.39–
8.42(m, 2H, pyridine-4,6), 8.25–8.28(m, 1H, pyridine-5), 7.52–
7.605(m, 4H, phenyl-2, 3, 5, 6); Anal. Calc. for C14H9N5S: C, 60.2;
H, 3.25; N, 25.07; Found: C, 60.63; H, 3.22; N, 24.95%. IR (cmꢁ1
,
KBr pellets): 3325w, 3049w, 2998w, 1992w, 1916w, 1887w,
1809w, 1765w, 1732w, 1693w, 1651w, 1586m, 1571m, 1533w,
1514w, 1480s, 1460s, 1420s, 1380m, 1357m, 1335m, 1308w,
1290m, 1270m, 1244m, 1192m, 1172m, 1123m, 1096w, 1074w,
1049w, 1026m, 998w, 975s, 955s, 922m, 812s, 770s, 721w, 701s,
684s, 672s, 621m, 600m.
2. Experimental
2.1. Materials and general methods
All the other reagents used for the syntheses were commercially
available and employed without further purification. The interme-
diate of 3-phenyl-4-amino-5-sulfhydryl-1,2,4-triazole (a) was pre-
pared according to reported procedures [15]. IR spectra were
measured on a Brucker Equinox 55 FT-IR spectrometer with KBr
Pellets in the range of 4000–400 cmꢁ1. Elemental analyses of C, H
and N were performed on a Thermo Flash EA 1112-NCHS-O ana-
lyzer. 1H NMR data were collected using an INOVA-400 NMR
spectrometer. Chemical shifts are reported in relative to TMS.
Solid-state emission and excitation spectra of compounds were
measured using a Cary Eclips fluorescence spectrophotometer.
2.2.3. 4-phenyl-7-(pyridine-4-yl)-1,2,4-triazolo[3,4-b]-1,3,4-
thiadiazole(L3)
Ligand L3 were obtained by the similar method described for L1.
Yield: ꢂ55%. m.p. 234–236 °C. 1H NMR (CDCl3): d: 8.90(d, 2H,
J = 4.4 Hz, pyridine-2,6), 7.86(d, 2H, J = 4.4 Hz, pyridine-3,5),
8.40(dd, 2H, J = 1.6, 6.8 Hz phenyl-2, 6), 7.55–7.61(m, 3H, phenyl-
3, 4, 5); Anal. Calc. for C14H9N5S: C, 60.2; H, 3.25; N, 25.07; Found:
C, 60.63; H, 3.22; N, 24.95%. IR (cmꢁ1, KBr pellets): 3429m, 3074w,
3038w, 2897w, 2552w, 2447w, 1974w, 1944w, 1825w, 1779w,
1708w, 1677w, 1625w, 1597s, 1560w, 1513w, 1491w, 1467s,
1438s, 1415s, 1380m, 1359m, 1330m, 1311m, 1292m, 1268m,
1245m, 1217m, 1184m, 975s, 959s, 856w, 820s, 774s, 699s,
685s,651m, 610s, 597s.
2.2. Synthesis of L1–L4
2.2.1. 4,7-diphenyl-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazole (L1)
The route of synthesis is shown in Chart 2, the intermediate of
3-phenyl-4-amino-5-sulfhydryl-1,2,4-triazole (a) (5 mmol) and
benzoic acid (5 mmol) was added to freshly distilled POCl3
(20 mL). After heating in an oil bath at 120° for 8 h, then removing
excess POCl3 under depress pressure. Poured reactor into cold
water, neutralized with NaOH to give ligand L1, recrystallized from
absolute ethanol to give ligand L1 as white crystals. Yield: ꢂ65%.
m.p. 209–211 °C. 1H NMR (CDCl3): d: 7.50–8.44(m, 10H, phenyl);
Anal. Calc. for C15H10N4S: C, 64.73; H, 3.62; N, 20.13; Found: C,
64.92; H, 3.54; N, 20.24%. IR (cmꢁ1, KBr pellets): 3061w, 3028w,
2895w, 1971w, 1903w, 1809w, 1774w, 1685w, 1655w, 1595w,
1578w, 1512m, 1469s, 1436m, 1380m, 1358m, 1311m, 1289m,
1268m, 1238m, 1175w, 1155w, 1108w, 1075m, 1022w, 1000m,
975s, 954m, 919m, 798w, 772s, 765s, 714w, 683s, 651m, 617m,
606m.
2.2.4. 4-(pyridine-3-yl)-7-(pyridine-4-yl)-1,2,4-triazolo[3,4-b]-1,3,4-
thiadiazole(L4)
Ligand L4 were obtained by the similar method described for L1.
Yield: ꢂ45%. m.p. 231–232 °C. 1H NMR (CDCl3): d: 7.26–9.67(m,
8H, pyridine); Anal. Calc. for C13H8N6S: C, 55.70; H, 2.88; N,
29.98; Found: C, 55.64; H, 2.93; N, 28.95%. IR (cmꢁ1, KBr pellets):
3030m, 2894w, 2433w, 1942w, 1698w, 1629w, 1595s, 1571s,
1523s, 1510s, 1486s, 1470s, 1455s, 1409s, 1379s, 1332m, 1310m,
1278s, 1248s, 1220m, 1191s, 1119m, 1095m, 1066m, 1028m,
979s, 962s, 825s, 807s, 723m, 703s, 692s, 653s, 614s, 600s, 497m,
408m.
N
N
N N
N
N
N N
N
N
S
N
S
N
N
S
S
N
N
N
N
N
N
N
L1
L2
L3
L4
Chart 1.

218
D.-Z. Wang et al. / Polyhedron 42 (2012) 216–226
Table 1
Crystal data and structure refinement summary for complexes 1–7.
1
2
3
4
Formula
Formula weight
Crystal system
Space group
T/K
C
30H20Cl2N8S2Zn
C30H20Cl2N8S2Co
686.49
C28H22Cl2N10O10S2Cd
905.98
monoclinic
P21/c
C28H24N12O8S2Cd
833.13
692.93
triclinic
P1
293(2)
triclinic
triclinic
ꢀ
ꢀ
ꢀ
P1
P1
293(2)
293(2)
293(2)
a (Å)
b (Å)
c (Å)
8.9844(18)
11.136(2)
16.275(3)
92.85(3)
99.72(3) deg
112.03(3)
1476.5(5)
2
9.0111(18)
11.096(2)
16.269(3)
92.58(3)
99.92(3)
112.12(3)
1473.6(5)
2
9.2872(19)
11.644(2)
16.208(3)
90.00
101.70(3)
90.00
1716.4(7)
2
1.629
7.7599(16)
9.5188(19)
12.220(2)
71.06(3)
86.03(3)
68.84(3)
795.0(3)
1
a
(°)
b (°)
c
(°)
V (Å3)
Z
D (g cmꢁ3
l
)
1.559
1.191
1.547
0.942
1.736
0.890
(mmꢁ1)
0.970
F(000)
704
698
844
418
Measured reflections
Observed reflections
Ra/wRb
14612
6697
0.0330/0.1284
14562
6697
0.0370/0.1581
12592
3927
0.0539/0.1782
6133
2804
0.0354/0.1124
5
6
7
Formula
Formula weight
Crystal system
Space group
T (K)
a (Å)
b (Å)
c (Å)
C
29H20Cl2N12O6S2Cu
C31H32BF4N10O4S2Cu
823.03
monoclinic
P2(1)/c
C26H16N14O6S2 Cd
797.06
831.12
triclinic
P1
triclinic
ꢀ
P1
293(2)
7.3047(15)
10.152(2)
11.641(2)
91.98(3)
105.00(3)
105.94(3)
796.6(3)
1
293(2)
293(2)
12.724(3)
14.129(3)
20.078(4)
90
100.01(3)
90
3554.5(12)
4
1.514
7.5156(15)
8.6668(17)
13.067(3)
104.01(3)
101.00(3)
102.68(3)
778.4(3)
1
a
(°)
b (°)
c
(°)
V (Å3)
Z
D (g cmꢁ3
l
)
1.730
1.051
1.700
0.902
(mmꢁ1
)
0.805
F(000)
420
1636
398
Measured reflections
Observed reflections
Ra/wRb
7876
5943
0.0431/0.1211
27885
6575
0.0773/0.2729
7671
3536
0.0358/0.1028
P
P
a
R = (||F0|–|FC||)/ |F0|.
P
P
b
wR = [ w(|F0|2—|FC|2)2/ w(F02)]1/2
.
2.3. Synthesis of complexes 1–7
2.3.1. Zn(L1)2Cl2 (1)
Complex 1 was prepared by dissolving ZnCl2ꢀ4H2O (0.3 mmol)
and L1 (0.3 mmol) in ethanol solution (15 mL). Colorless plate-
shaped crystals were formed after several days with the evapora-
tion of the solvent (ca. 40% yield based on L1). Anal. Calc. for
2.3.3. {[Cd(L2)2(H2O)2]ꢀ(ClO4)2} (3)
1
Complex 3 was obtained by a procedure similar to that for 1
except for using Cd(ClO4)2ꢀ6H2O instead of ZnCl2ꢀ4H2O and L2 in-
stead of L1 (ca. 25% yield based on L2). Anal. Calc. for
C
28H22CdCl2N10O10S2: C, 37.12; H, 2.45; N, 15.46. Found: C,
37.36; H, 2.49; N, 15.41%. IR (cmꢁ1, KBr pellets): 3386s, 3083m,
2495w, 2165w, 1973w, 1907w, 1826w, 1777w, 1629m, 1603m,
1576m, 1527m, 1472s, 1422s, 1380m, 1342m, 1317m, 1296m,
1279m, 1254m, 1199m, 1182m, 1092s, 1029s, 994s, 958s, 925m,
818m, 772m, 720m, 691s, 624s, 502m, 414m.
C
30H20ZnCl2N8S2: C, 52.00; H, 2.91; N, 16.17. Found: C, 51.89; H,
2.79; N, 16.26%. IR (cmꢁ1, KBr pellets): 3433w, 3049w, 2576w,
1965w, 1892w, 1809w, 1761w, 1685w, 1594w, 1533w, 1516w,
1473s, 1440s, 1370m, 1336m, 1314m, 1290m, 1270s, 1236m,
1187m, 1158m, 1126m, 1098m, 1072m, 1044m, 1012m, 961m,
922m, 850w, 811w, 764s, 687s, 651m, 604s, 501m, 470m, 412m.
2.3.4. Cd(L2)2(NO3)2(H2O)2 (4)
Colorless crystals of 4 suitable for X-ray analysis were obtained
by the similar method described for 3, except for using
Cd(NO3)2ꢀ6H2O instead of Cd(ClO4)2ꢀ6H2O (ca. 35% yield based on
L2). Anal. Calc. for C28H22CdN12O8S2: C, 40.46; H, 2.67; N, 20.22.
Found: C, 40.22; H, 2.69; N, 20.17%. IR (cmꢁ1, KBr pellets):
3181m, 3067m, 2449w, 2337w, 1893w, 1811w, 1748w, 1653m,
1597m, 1535w, 1514w, 1465s, 1422s, 1350m, 1301s, 1199m,
1133m, 1036m, 982m, 961m, 813m, 765m, 690s, 638m, 609m,
500m, 411m.
2.3.2. Co(L1)2Cl2 (2)
Blue crystals of 2 suitable for X-ray analysis were obtained by
the similar method described for 1, except for using CoCl2ꢀ6H2O in-
stead of ZnCl2ꢀ4H2O (ca. 30% yield based on L1). Anal. Calc. for
C30H20CoCl2N8S2: C, 52.49; H, 2.94; N, 16.32. Found: C, 52.37; H,
2.87; N, 16.29%. IR (cmꢁ1, KBr pellets): 3422w, 3049w, 1964w,
1892w, 1809w, 1762w, 1686w, 1594w, 1532w, 1516m, 1491m,
1473s, 1440s, 1370m, 1346m, 1335m, 1315m, 1292m, 1270s,
1239m, 1214m, 1188m, 1159m, 1126m, 1099m, 1073m, 1041m,
1024m, 1014s, 962s, 924m, 850w, 813m, 764s, 713m, 688s, 673m,
653m, 606s, 504m, 472m, 418m.
2.3.5. {[Cu(L3)2(NO3)2]ꢀ(CH2Cl2)} (5)
1
A solution of Cu(NO3)2ꢀ3H2O (0.10 mmol) in methanol solution
(8 mL) was layered onto a solution of L3 (0.10 mmol) in CH2Cl2
(8 mL). Blue plate-shaped crystals of complex 5 were formed after

D.-Z. Wang et al. / Polyhedron 42 (2012) 216–226
219
Table 2
several days with the evaporation of the solvent (ca. 30% yield
based on L3). Anal. Calc. for C29H20Cl2N12O6S2Cu: C, 41.91; H,
2.42; N, 20.22. Found: C, 41.79; H, 2.69; N, 20.12%. IR (cmꢁ1, KBr
pellets): 3499m, 3069w, 2926w, 2426w, 1764w, 1614m, 1599w,
1535w, 521m, 1502s, 1476s, 1445s, 1420s, 1384s, 1284s, 1221w,
1183w, 1131w, 1062w, 1025m, 977m, 921w, 866w, 835m, 816m,
769m, 716m, 691s, 667w, 610m.
Selected bond distances (Å) and Angles (°) for complexes 1–7.
Complex 1
Zn(1)–N(5)
Zn(1)–Cl(2)
N(5)–Zn(1)–N(1)
N(1)–Zn(1)–Cl(2)
N(1)–Zn(1)–Cl(1)
2.020(2)
2.220(1)
115.6(1)
110.3(9)
101.2(9)
Zn(1)–N(1)
Zn(1)–Cl(1)
N(5)–Zn(1)–Cl(2)
N(5)–Zn(1)–Cl(1)
Cl(2)–Zn(1)–Cl(1)
2.033(3)
2.228(1)
101.1(9)
109.6(8)
119.8(5)
Complex 2
2.3.6. {[Cu(L3)2(OH)(MeOH)]ꢀ(MeOH)2ꢀBF4} (6)
Co(1)–N(5)
Co(1)–Cl(1)
N(5)–Co(1)–N(1)
N(1)–Co(1)–Cl(1)
N(1)–Co(1)–Cl(2)
2.006(3)
2.228(1)
117.4(1)
100.5(9)
109.5(8)
Co(1)–N(1)
Co(1)–Cl(2)
N(5)–Co(1)–Cl(1)
N(5)–Co(1)–Cl(2)
Cl(1)–Co(1)–Cl(2)
2.009(2)
2.235(1)
110.8(9)
100.6(9)
119.1(5)
1
Blue crystals of 6 suitable for X-ray analysis were obtained by
the similar method described for 5, except for using Cu(BF4)2ꢀH2O
instead of Cu(NO3)2ꢀ3H2O (ca. 30% yield based on L3). Anal. Calc.
for C31H32BF4N10O4S2Cu: C, 45.23; H, 3.92; N, 17.02. Found: C,
45.29; H, 3.87; N, 17.14%. IR (cmꢁ1, KBr pellets): 3589m, 3337m,
3108m, 1654w, 1615m, 1531w, 1499m, 1474s, 1422s, 1378w,
1332m, 1293m, 1272m, 1221w, 1055s, 1012s, 973s, 877w, 837m,
823m, 767s, 691s, 674m, 608s.
Complex 3
Cd(1)–O(1W)
2.289(4)
2.353(4)
86.4(2)
87.7(2)
86.9(2)
Cd(1)–N(1)
2.330(4)
Cd(1)–N(5)#2
N(1)#1–Cd(1)–N(5)#2
O(1W)–Cd(1)–N(1)
O(1W)#1–Cd(1)–N(5)#2
O(1W)#1–Cd(1)–N(1)
N(1)–Cd(1)–N(5)#2
O(1W)–Cd(1)–N(5)#2
92.3(2)
93.6(2)
93.1(2)
Complex 4
Cd(1)–O(1W)
Cd(1)–N(1)
O(2)–Cd(1)–N(1)
O(1W)#1–Cd(1)–O(2)#1
O(1W)#1–Cd(1)–N(1)
2.3.7. [Cd(L4)2(NO3)2]1 (7)
2.289(3)
2.337(3)
89.7(1)
98.9(1)
90.7(1)
Cd(1)–O(2)
2.323(3)
Complex 7 was obtained by a procedure similar to that for 1 ex-
cept for using Cd(NO3)2ꢀ6H2O instead of ZnCl2ꢀ4H2O and L4 instead
of L1 (ca. 35% yield based on L4). Anal. Calc. for C26H16CdN14O6S2: C,
O(1W)–Cd(1)–O(2)#1
O(2)–Cd(1)–N(1)#1
O(1W)–Cd(1)–N(1)
81.1(1)
90.3(1)
89.29(1)
39.18; H, 2.02; N, 24.60. Found: 38.98; H, 2.03; N, 24.63%. IR (cmꢁ1
,
Complex 5
KBr pellets): 3664w, 3445w, 3102w, 3071m, 3032w, 2833w,
2456w, 2322w, 1955w, 1738w, 1600s, 1586m, 1534w, 1518m,
1477s, 1427s, 1302s, 1251s, 1217m, 1194m, 1121m, 1099m,
1050m, 1032s, 1004s, 970s, 947m, 862m, 818s, 732m, 704s,
655m, 635s, 608s, 527w, 501w, 473w, 427m, 406m.
Caution! Perchlorate complexes of metal ions in the presence of
organic ligands are potentially explosive. Only a small amount of
material should be used and handled with care.
Cu(1)–N(8)
1.958(4)
2.029(3)
2.184(4)
97.71(1)
89.4(1)
129.7(1)
85.6(1)
78.2(1)
Cu(1)–N(1)
Cu(1)–O(6)
1.976(4)
2.167(3)
Cu(1)–N(12)#1
Cu(1)–O(3)
N(8)–Cu(1)–N(12)#1
N(8)–Cu(1)–O(6)
N(12)#1–Cu(1)–O(6)
N(1)–Cu(1)–O(3)
O(6)–Cu(1)–O(3)
N(1)–Cu(1)–N(12)#1
N(1)–Cu(1)–O(6)
N(8)–Cu(1)–O(3)
N(12)#1–Cu(1)–O(3)
89.5(1)
88.9(1)
86.2(1)
151.7(1)
Complex 6
Cu–O(1)
1.902(3)
1.997(6)
2.303(4)
85.7(2)
94.1(2)
84.9(2)
96.5(2)
Cu–N(1)
1.988(6)
1.998(5)
Cu–N(6)
Cu–N(5)#1
Cu–O(1)#2
2.4. X-Ray crystallography
O(1)–Cu–N(1)
N(1)–Cu–N(5)#1
O(1)–Cu–O(1)#2
N(6)–Cu–O(1)#2
O(1)–Cu–N(6)
84.7(2)
95.9(2)
95.2(2)
93.4(2)
N(6)–Cu–N(5)#1
N(1)–Cu–O(1)#2
N(5)#1–Cu–O(1)#2
Single-crystal X-ray diffraction measurements for complexes 1–
7 were carried out on a R-AXIS SPIDER diffractometer equipped
with a graphite crystal monochromator situated in the incident
beam for data collection at 293(2) K. The determinations of unit
cell parameters and data collections were performed with MoKa
radiation (k = 0.71073) and unit cell dimensions were obtained
with least-squares refinements. The program SAINT [16] was used
for integration of the diffraction profiles. All the structures were
solved by direct methods using the SHELXS program of the SHELXTL
package and refined by full-matrix least-squares methods with
SHELXL [17]. Semi-empirical absorption corrections were carried
out using SADABS program [18]. Metal atoms in the complexes were
located from the E-maps and other non-hydrogen atoms were lo-
cated in successive difference Fourier syntheses and refined with
anisotropic thermal parameters on F2. The hydrogen atoms of the
ligand were generated geometrically; and the hydrogen atoms of
the water molecules were located from difference maps and
refined with isotropic temperature factors. Crystal data and struc-
ture refinement parameters details for complexes 1–7 are given in
Table 1.
Complex 7
Cd(1)–N(1)
2.289(1)
2.361(8)
2.390(9)
88.6(3)
80.1(3)
97.5(3)
86.7(3)
73.9(3)
Cd(1)–N(7)
2.326(7)
2.353(7)
2.437(8)
100.7(3)
81.8(3)
93.6(3)
91.1(3)
106.3(3)
Cd(1)–O(1)
Cd(1)–O(4)
Cd(1)–N(5)#1
Cd(1)–N(12)#2
N(7)–Cd(1)–N(12)#2
N(1)–Cd(1)–O(1)
N(1)–Cd(1)–O(4)
N(1)–Cd(1)–N(5)#1
O(1)–Cd(1)–N(5)#1
N(7)–Cd(1)–O(1)
N(7)–Cd(1)–O(4)
N(1)–Cd(1)–N(12)#2
N(7)–Cd(1)–N(5)#1
O(4)–Cd(1)–N(5)#1
Symmetry code for 3: #1 ꢁx + 1,ꢁy,ꢁz; #2 x ꢁ 1/2,ꢁy + 1/2,z ꢁ 1/2; #3 ꢁx + 3/
2,y ꢁ 1/2,ꢁz + 1/2. for 4: #1 ꢁx,ꢁy,ꢁz + 2. for 5: #1 x ꢁ 1,y ꢁ 1,z. for 6: #1 x,ꢁy + 3/
2,z + 1/2; #2 ꢁx + 1,ꢁy + 1,ꢁz + 1. for 7: #1 x,y + 1,z; #2 x,y ꢁ 1,z.
The infrared spectra of 1–7 exhibits characteristic absorptions
for corresponding ligands with a slight shift due to coordination.
The absorption band at about 1350 cmꢁ1
,
1384 cmꢁ1 and
1302 cmꢁ1 indicates the existence of the NO3 anion in 4, 5 and
7. The characteristic bands of the free perchlorate ion appear at
1092 cmꢁ1 and 624 cmꢁ1 in 3. The absorption band at 1055 cmꢁ1
ꢁ
indicates the existence of the BF4 anion in 6. L1–L4 and 1–7 all
ꢁ
exhibited absorptions corresponding to the framework vibrations
of aromatic rings at about 1420–1650 cmꢁ1
.
3. Results and discussion
3.1. Synthesis and general characterization
3.2. Description of the crystal structure
L1–L4 was prepared in higher yield as white crystalline solid by
the reaction of 3-phenyl-4-amino-5-sulfhydryl-1,2,4-triazole (a)
with different aromatic carboxylic acid. The structures of L1–L4
were determined by 1H NMR, IR, elemental analysis. All the com-
plexes 1–7 are air stable at room temperature.
3.2.1. Zn(L1)2Cl2 (1) and Co(L1)2Cl2 (2)
Structural analyses were carried out and similar cell parameters
of complexes 1 and 2 (Table 1) indicate that they have similar struc-
ture. Compounds 1 and 2 have the general formula of M(L1)2Cl2

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D.-Z. Wang et al. / Polyhedron 42 (2012) 216–226
Fig. 1. View of (a) the coordination environment of ZnII ions in 1 (b) the 1-D chain by inter-plane p p stacking interactions of 1 (c) the 1-D chain formed by the C–H Cl and C–H
N weak interactions of 1 (H atoms omitted for clarity).
[M = Zn (1), M = Co (2)]. In 1, the coordination environment of ZnII
ion is also the same as that of CoII ion in 2. Therefore, we just de-
scribe structure of complex 1 later in this text in detail relatively.
linked to two distinct triazole N donors of two L1 ligands and
two chlorine atoms, the Zn(1)–N(5) and Zn(1)–N(1) bond distances
are 2.020(2) and 2.033(3) Å, respectively, which are in the normal
range [19]. Two L1 ligands all adopt monodentate coordination
mode. All the atoms of each ligand L1 are almost in the same plane,
the mean deviations from the planes of two ligands are ca. 0.0649
and 0.0497 Å, the dihedral angles between planes of two ligands L1
ꢀ
Complex 1 crystallizes in P1 space group and the selected bond
distances and angles were listed in Table 2. The X-ray diffraction
analysis shows that 1 has a mononuclear structure (see Fig. 1a).
The ZnII center features a distorted tetrahedral geometry, and

D.-Z. Wang et al. / Polyhedron 42 (2012) 216–226
221
centroid–centroid separations are 3.378 and 3.290 Å, respectively
(Fig. 1b).
In addition, the C–H Cl and C–H N weak interactions were ob-
served between adjacent mononuclear structures. The distance of
C(4) Cl(2) is 3.404 Å with the angle C(4)–H(4B) Cl(2) being
101.46°, the distance of C(7) N(2) is 3.494 Å with the angle C(7)–
H(7A) N(6) being 156.55°, Therefore, mononuclear structures were
further assembled by the C–H Cl and C–H N weak interactions into
an infinite a supramolecular chain along the other direction
(Fig. 1c).
The mononuclear structure of complex 2 shows in Fig. 2. The
mean deviations from the planes of two ligands in 2 are ca.
0.0505 and 0.0620 Å, the dihedral angles between planes of two li-
gands L1 is 104.2°. Similarly, inter-plane p p stacking interactions
and the C–H Cl and C–H N weak interactions were observed in 2,
the centroid–centroid separations are 3.369 and 3.278 Å, respec-
tively. The distance of C(19) Cl(2) is 3.404 Å with the angle
C(19)–H(19A) Cl(1) being 100.79°, the distance of C(22) N(2) is
3.489 Å with the angle C(22)–H(22A) N(2) being 156.60°. The
Fig. 2. View of the coordination environment of CoII ions in 2 (H atoms omitted for
clarity).
is 104.9°. It should be pointed out that two planes of ligands from
the adjacent mononuclear structure are almost parallel to each
other, these mononuclear structure were further extended into
1-D chain by inter-plane p p stacking interactions between the
ligands planes from adjacent mononuclear structure. The
Fig. 3. View of (a) the coordination environment of CdII ions in 3 (b) 2-D (4,4) network structure of 3 (c) the 3-D supramolecular network by O–Hꢀ ꢀ ꢀO hydrogen-bonding
interactions (H atoms omitted for clarity).

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D.-Z. Wang et al. / Polyhedron 42 (2012) 216–226
Fig. 4. View of (a) the coordination environment of CdII ions in 4 (b) the 1-D chain by O–H. . .O hydrogen bonding interactions of 4 (c) the 2-D supramolecular sheet formed by
the O–H. . .O and O–H N weak interactions of 4 (H atoms omitted for clarity).
mononuclear structure were further extended into a chain along
different directions by inter-plane p p stacking interactions and
the C–H Cl and C–H N weak interactions.
the equatorial plane and two O atoms from water molecules
[Cd(1)–O(1W) = 2.288(5) Å] at the axial positions to complete its
distorted octahedron coordination geometry with the coordination
angles varying from 86.36(15)° to 180.00° (Fig. 3a and Table 2).
Each L2 ligand links two CdII ions and in turn each CdII ion con-
nects four ligands forming a layer structure with (4, 4) grid units, in
which all the CdII ions are located in one plane (Fig. 3b). From
Fig. 3b, each (4, 4) grid unit is constructed by four ligands acting
as four edges and four CdII ions as four vertexs. All the lengths of
the edges are equal (the edges are 10.289 Å) and the orthogonal
distances are 11.644 and 16.968 Å, respectively. The uncoordinated
3.2.2. {[Cd(L2)2(H2O)2]ꢀ(ClO4)2} (3)
1
Complex 3 is a neutral rhombohedral grid with (Fig. 3b) a (4, 4)
topology (Fig. 3c). The centrosymmetric unit contains a CdII center,
two L2 ligands and two water molecules. The CdII center is coordi-
nated to two N atoms of 1,2,4-triazolo[3,4-b]-1,3,4-thiadiazole
from distinct L2 ligands [Cd(1)–N(1) = 2.333(5) Å], two N atoms
of pyridine from distinct L2 ligands [Cd(1)–N(5) = 2.356(5) Å] in

D.-Z. Wang et al. / Polyhedron 42 (2012) 216–226
223
Fig. 5. View of (a) the coordination environment of CuII ions in 5 (b) the 1-D supramolecular chain (H atoms omitted for clarity).
ꢁ
ClO4 anions serving as counteranion, and locate at the cavities of
the sheets and form O–Hꢀ ꢀ ꢀO hydrogen-bonding with the coordi-
nated water molecules of the complex to give a three-dimensional
framework [Oꢀ ꢀ ꢀO separations are 2.65 and 2.81 Å, respectively].
The hydrogen-bonding parameters (Å, °) were listed in Table 2.
Obviously, the structural difference of 3 and 4 is attributabꢁle to
the difference of counter anions, namely, ClO4ꢁ for 3 and NO3 for
4.
3.2.4. {[Cu(L3)2(NO3)2]ꢀ(CH2Cl2)} (5)
1
The structure of 5 is a 1-D neutral coordination chain. As shown
in Fig. 5b, the six-coordinated environment of CuII (Fig. 5a) center
is as follows in detail: three nitrogen atoms belonging to three dis-
tinct L3 ligands [the Cu–N lengths are all within normal range and
at the range of from 1.958(4) to 2.029(3) Å] and three oxygen
3.2.3. Cd(L2)2(NO3)2(H2O)2 (4)
The structure of 4 consists of a centrosymmetric mononuclear
neutral molecule Cd(L2)2(NO3)2(H2O)2 (Fig. 4a). In the mononu-
clear unit, the six-coordinated environment of Cd(II) ion is as fol-
lows in detail: two oxygen atoms from two water molecules and
two nitrogen atoms of pyridine from two distinct ligands L2
[adopting N-terminal coordination mode] are coordinated to the
Cd(II) ion; meanwhile, the last two coordination sites are occupied
by two oxygen atoms from two different NO3ꢁ anions, respectively.
The L2 ligand adopts monodentate coordination mode. All the
atoms of the ligand L2 are amost (almost) in the same plane, the
mean deviations from the planes of the ligand is ca. 0.0783 Å. It
should be noted that an 1-D structure along a direction is formed
through intermolecular O–H. . .O hydrogen bonding interactions.
ꢁ
ꢁ
atoms from two distinct NO3 anions [one NO3 anion adopted
bidentate chelating coordination mode, Cu–O lengths of 2.184(4)
ꢁ
and 2.506 Å, respectively, another NO3 anion adopted monoden-
tate coordination mode, Cu–O lengths of 2.167(3) Å] are coordi-
nated to the CuII center. The selected bond distances and angles
were listed in Table 2. In 5, two unequivalent L3 were observed,
one L3 adopted bidentate bridge coordination mode, and link the
complex 5 into a supramolecular chain, another monodentate
coordination mode. The distance of the two CuII center was
10.756 Å.
ꢁ
As shown in Fig. 4b, the O(3) atom of the NO3 anions serves as
the acceptors to form O(1w)–H(1). . .O(3) intermolecular hydrogen
bonds with coordinated water molecules. The O. . .O distance of
2.806 Å fall into the normal range of hydrogen bond interactions.
In addition, the O–H N hydrogen bonding interactions were
observed between adjacent a supramolecular chain formed by
the O–H. . .O hydrogen bonding interactions (Fig. 4b). The distance
of O(1W) N(5) is 2.834 Å, Therefore, the supramolecular chain were
further assembled by the O–H N hydrogen bonding interactions
into an infinite 2-D supramolecular network structure (Fig. 4c).
3.2.5. {[Cu(L3)2(OH)(MeOH)]ꢀ(MeOH)2ꢀBF4} (6)
1
To investigate the influence of counter-anions in constructing
coordination frameworks, 6 was obtained by the reaction of L3
with Cu(BF4)2ꢀH2O instead of Cu(NO3)2ꢀ3H2O used for 5. Complex
6 crystallizes in the monoclinic system space group, P2(1)/c. Se-
lected bond lengths and angles were shown in Table 2. X-ray sin-
gle-crystal diffraction analyses revealed that 6 have an infinite
square grid structure consisting of the dinuclear Cu2O2 units, Cu–
O2–Cu (Ci symmetry), and L3 ligands. The CuII center has a distorted

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D.-Z. Wang et al. / Polyhedron 42 (2012) 216–226
Fig. 6. View of (a) the coordination environment of CuII ions in 6 (b) the binuclear structure unit of 6 (c) 2-D (4,4) network structure of 6 (H atoms omitted for clarity).
octahedron coordination geometry, which is formed by three nitro-
gen donor atoms of distinct ligands L3, two symmetrical O atoms
from OH– anions and one O atom of MeOH molecules (Fig. 6a).
The CuII donor bond distances are all within normal range [Cu–
N(1) = 1.988(6) Å, Cu–N(6) = 1.997(6) Å, Cu–N(5) = 1.998(5) Å, Cu–
O(1) = 1.902(3) Å, Cu–O(1)#2 = 2.303(4) Å, Cu–O(3)#2 = 2.567 Å]
(symmetry code: #2 ꢁx + 1,ꢁy + 1,ꢁz + 1) (Table 2). The bond an-
gles around the CuII ions are in the range of 84.67(19)–178.2(2)°.
The CuII centers bridged by two OHꢁ anions are separated by a
relatively short distance of 3.113 Å. It is well below the summed
Van der Waals radii of two copper atoms (2.8 Å), this distance is
longer than 2.8 Å, indicating there is no Cu. . .Cu interaction. Two
O atoms link two CuII ions to form a dinuclear unit Cu2O2
(Fig. 6b). At the same time, the dinuclear Cu2O2 units are intercon-
nected by four L3 ligands via copper-nitrogen bonds to form a 2-D
layer with (4, 4) topology (Fig. 6c). The resulting 2-D layers are
packed parallel to complete the final 3-D structure. No obvious
p–p interactions are found between the layers.
3.2.6. [Cd(L4)2(NO3)2]1 (7)
As shown in Fig. 7, complex 7 crystallizes in P1 space group, as
shown in Fig. 7 and 7 has 1-D neutral coordination chain. The CdII

D.-Z. Wang et al. / Polyhedron 42 (2012) 216–226
225
Fig. 7. View of (a) the coordination environment of CdII ions in 7 (b) the 1-D supramolecular chain (H atoms omitted for clarity).
ion is six-coordinated to two oxygen atoms of two distinct nitrate
anions [adopting monodentate coordination mode, Cd(1)–
O(1) = 2.361(8) Å, Cd(1)–O(4) = 2.353(7) Å], two N donors of pyri-
dine from two distinct ligands L4 [Cd(1)–N(5) = 2.390(9) Å,
Cd(1)–N(12) = 2.437(8) Å] and two N donors of triazoles ring from
two distinct L4 ligands [Cd(1)–N(1) = 2.289(10) Å, Cd(1)–
N(7) = 2.326(7) Å] to form a distorted octahedral geometry. The se-
lected bond distances and angles were listed in Table 2. In 7, all L4
ligands are unequivalent, and adopt a bidentate bridged coordina-
tion mode. The distance of the two N atoms coordinated to CdII
center was unequal, 5.656 and 5.580 Å, respectively, and the adja-
cent CdII centers are linked by two bridging L4 in two different
directions to form 1-D chain [the non-bonding Cd/Cd distances
are 8.667 Å].
at 372 nm. Difference from 4, complex 3 exhibits two intense emis-
sion bands at 411 and 435 nm upon excitation at 380 nm. L4 exhib-
its an intense blue fluorescent emission band at 439 nm upon
excitation at 370 nm. Complex 7 exhibits two intense emission
bands at 406 and 461 nm upon excitation at 375 nm. Compared
with that of the free ligand, complexes in the solid state have a
similar blue shift. This blue shift was respect to the free ligands
may be caused by the coordination or the changes of conformation
of ligands [21].
3.4. Conclusion
A series of new d10 metals (Zn and Cd) and transition metals (Cu
and Co) metal-organic complexes with 4,7-diphenyl-1,2,4-tria-
zolo[3,4-b]-1,3,4-thiadiazole (L1), 4-phenyl-7-(pyridine-3-yl)-1,2,
4-triazolo[3,4-b]-1,3,4-thiadiazole (L2), 4-phenyl-7-(pyridine-4-
yl)-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazole (L3) and 4-(pyridine-
3-yl)-7-(pyridine-4-yl)-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazole (L4)
have been synthesized and structurally characterized. The influ-
ences of the locality and amount of coordination atoms in the same
ligands’ framework and counteranions on the resultant structures
of their metal complexes are briefly discussed. Some intra-molec-
ular and/or inter-molecular weak interactions, such as hydrogen
bonding, also play important roles in the formation of these com-
plexes, especially in the aspects of linking the discrete subunits
and low-dimensional entities into high-dimensional supramolecu-
lar networks. Moreover, the fluorescence properties of ligands L1,
L2, L4 and corresponding ZnII/CdII complexes display strong blue
3.3. Luminescent properties
Aromatic organic molecules and mixed inorganic–organic hy-
brid coordination polymers are promising luminescent materials
for their potential applications, such as light-emitting materials
(LEDs) [20]. The emission spectra of L1, L2, L4 and complexes 1, 3,
4 and 7 in the solid state at room temperature were investigated
(see Supplementary 1). L1 exhibits an intense blue fluorescent
emission band at 422 nm upon excitation at 370 nm. Complex 1
exhibits weak blue fluorescent emission bands at 397 nm upon
excitation at 350 nm. L2 exhibits an intense blue fluorescent emis-
sion band at 450 nm upon excitation at 396 nm. Complexes 4 dis-
play strong fluorescent emission bands at 427 nm upon excitation

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D.-Z. Wang et al. / Polyhedron 42 (2012) 216–226
(2006) 2126;
fluorescent emission at room temperature. This approach may be
useful for the construction of a variety of new transition metal
complexes and luminescent coordination polymers with novel
structures that have the potential of leading to new fluorescent
materials.
(e) X.L. Tong, D.Z. Wang, T.L. Hu, W.C. Song, Y. Tao, X.H. Bu, Cryst. Growth Des.
9 (2009) 2280;
(f) T.L. Hu, J.R. Li, C.S. Liu, X.S. Shi, J.N. Zhou, X.H. Bu, J. Ribas, Inorg. Chem. 45
(2006) 162.
[4] N.A. Negm, M.F. Zaki, Colloids Surf., B 64 (2008) 179.
[5] (a) P. Sood, A. Chandrasekaran, R.O. Day, R.R. Holms, Inorg. Chem. 37 (1998)
3747;
(b) D.F. Weng, W.H. Mu, X.J. Zheng, D.C. Fang, L.P. Jin, Inorg. Chem. 47 (2008)
1249.
Acknowledgments
[6] D. Braga, F. Grepioni, Coord. Chem. Rev. 183 (1999) 19.
[7] (a) A.J. Blake, N.R. Champness, P. Hubberstey, W.S. Li, M.A. Withersby, M.
Schröder, Coord. Chem. Rev. 183 (1999) 139;
This work was financially supported by the National Natural
Science Funds of XinJiang, China (No. 2011211A009) and
supported by the Open Project Program of Xinjiang Laboratory of
Advanced Functional Materials, China (XJDX0902-2010-02).
(b) L. Carlucci, G. Ciani, P. Macchi, D.M. Proserpio, Chem. Commun. (1998)
1837;
(c) H.P. Wu, C. Janiak, G. Rheinwald, H. Lang, J. Chem. Soc., Dalton Trans.
(1999) 183;
(d) D.K. Cao, Y.Z. Li, Y. Song, L.M. Zheng, Inorg. Chem. 44 (2005) 3599.
[8] (a) M.J. Zaworotko, Chem. Commun. (2001) 1;
Appendix A. Supplementary data
(b) D.Z. Wang, T.L. Hu, J.P. Zhao, X.H. Bu, CrystEngComm 12 (2010) 3587.
[9] (a) A. Mishra, W. Wernsdorfer, K.A. Abboud, G. Christou, J. Am. Chem. Soc. 126
(2004) 15648;
(b) F.A.A. Paz, J. Klinowski, Inorg. Chem. 43 (2004) 3948;
(c) J.R. Li, X.H. Bu, R.H. Zhang, Inorg. Chem. 43 (2004) 237.
[10] (a) J. Fan, W.Y. Sun, T. Okamura, Y.Q. Zheng, B. Sui, W.X. Tang, N. Ueyama,
Cryst. Growth Des. 4 (2004) 579;
(b) C.Y. Sun, X.J. Zheng, S. Gao, L.C. Li, L.P. Jin, Eur. J. Inorg. Chem. (2005) 4150.
[11] B. Ding, Y.Y. Liu, Y.Q. Huang, W. Shi, P. Cheng, D.Z. Liao, S.P. Yan, Cryst. Growth
Des. 9 (2009) 593.
[12] (a) S. Ferrer, J.G. Haasnoot, J. Reedijk, E. Müller, M.B.M.A. Cingi, M. Lanfranchi,
M. Lanfredi, J. Ribas, Inorg. Chem. 39 (2000) 1859;
CCDC 853771–853777 contains the supplementary crystallogra-
phic data for complexes 1ꢀZn(L1)2Cl2, 2ꢀCo(L1)2Cl2, 3ꢀ{[Cd(L2)2
(H2O)2]ꢀ(ClO4)2}1
,
4ꢀCd(L2)2(NO3)2(H2O)2, 5ꢀ{[Cu(L3)2(NO3)2]ꢀ
(CH2Cl2)} , 6ꢀ{[Cu(L3)2(OH)(MeOH)]ꢀ(MeOH)2ꢀBF4} and 7ꢀ[Cd(L4)2
1
1
(NO ) ]
3 2 1, respectively. These data can be obtained free of charge
via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the
Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge
CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail: deposit@ccdc.
cam.ac.uk. Supplementary data associated with this article can
be found, in the online version, at http://dx.doi.org/10.1016/
j.poly.2012.05.028.
(b) L. Yi, B. Ding, B. Zhao, P. Cheng, D.Z. Liao, S.P. Yan, Z.H. Jiang, Inorg. Chem.
43 (2004) 33;
(c) J.P. Zhang, X.M. Chen, Chem. Commun. (2006) 1689;
(d) Q.G. Zhai, X.Y. Wu, S.M. Chen, C.Z. Lu, W.B. Yang, Cryst. Growth Des. 6
(2006) 2126.
References
[13] (a) X.R. Meng, Y.L. Song, H.W. Hou, H.Y. Han, B. Xiao, Y.T. Fan, Y. Zhu, Inorg.
Chem. 43 (2004) 3528;
(b) X.R. Meng, Y.R. Liu, Y.L. Song, H.W. Hou, Y.T. Fan, Y. Zhu, Inorg. Chim. Acta
358 (2005) 3024;
[1] (a) O.K. Farha, A.M. Spokoyny, K.L. Mulfort, S. Galli, J.T. Hupp, C.A. Mirkin,
Small 5 (2009) 1727;
(c) B.L. Li, Y.F. Peng, B.Z. Li, Y. Zhang, Chem. Commun. (2005) 2333;
(d) B.Z. Li, Y.F. Peng, X.G. Liu, B.L. Li, Y. Zhang, J. Mol. Struct. 741 (2005) 235;
(e) Y.F. Peng, H.Y. Ge, B.Z. Li, B.L. Li, Y. Zhang, Cryst. Growth Des. 6 (2006) 994.
[14] D.Z. Wang, C.S. Liu, J.R. Li, L. Li, Y.F. Zeng, X.H. Bu, CrystEngComm 9 (2007) 287.
[15] N.D. Obushak, N.T. Pokhodylo, I.I. Krupa, V.S. Matiichuk, Russ. J. Org. Chem. 43
(8) (2007) 1223.
[16] Bruker AXS, SAINT Software Reference Manual, Madison, WI, USA, 1998.
[17] G.M. Sheldrick, SHELXTL NT Version 5.1. Program for Solution and Refinement of
Crystal Structures, University of Göttingen, Germany, 1997.
[18] G.M. Sheldrick, SADABS, Siemens Area Detestor Absorption Correction Program,
University of Gottingen, Gottingen, Germany, 1994.
[19] X.W. Wang, J.Z. Chen, J.H. Liu, Cryst. Growth Des. 7 (2007) 1227.
[20] (a) For examples: M. Altmann, U.H.F. Bunz, Angew. Chem., Int. Ed. 34 (1995)
569;
(b) M. Eddaoudi, J. Kim, N. Rosi, D. Vodak, J. Wachter, M. O’Keeffe, O.M. Yaghi,
Science 295 (2002) 469;
(c) X.H. Bu, M.L. Tong, H.C. Chang, S. Kitagawa, S.R. Batten, Angew. Chem., Int.
Ed. 43 (2004) 192;
(d) J.R. Li, D.J. Timmons, H.C. Zhou, J. Am. Chem. Soc. 131 (2009) 6368;
(e) X.M. Zhang, Z.M. Hao, W.X. Zhang, X.M. Chen, Angew. Chem., Int. Ed. 46
(2007) 3456;
(f) P. Horcajada, C. Serre, G. Maurin, N.A. Ramsahye, F. Balas, M. Vallet-Regí, M.
Sebban, F. Taulelle, G. Ferey, J. Am. Chem. Soc. 130 (2008) 6774;
(g) Y.F. Zeng, X. Hu, F.C. Liu, X.H. Bu, Chem. Soc. Rev. 38 (2009) 469;
(h) Q. Yu, Y.F. Zeng, J.P. Zhao, Q. Yang, X.H. Bu, Cryst. Growth Des. 10 (2010)
1878.
[2] (a) U. Beckmann, S. Brooker, Coord. Chem. Rev. 245 (2003) 17;
(b) R. Bronisz, Inorg. Chem. 46 (2007) 6733;
(b) U.H.F. Bunz, Chem. Rev. 100 (2000) 1605;
(c) R.L. Sang, L. Xu, Inorg. Chem. 44 (2005) 3731;
(d) D.M. Ciurtin, N.G. Pschirer, M.D. Smith, U.H.F. Bunz, H.C. Zur Loye, Chem.
Mater. 13 (2001) 2743;
(c) R. Bronisz, Inorg. Chem. 44 (2005) 4463;
(d) J. Fan, G.T. Yee, G. Wang, B.E. Hanson, Inorg. Chem. 45 (2006) 599.
[3] (a) X. Zhu, H.Y. Ge, Y.M. Zhang, B.L. Li, Y. Zhang, Polyhedron 25 (2006) 1875;
(b) N. Masciocchi, G.A. Ardizzoia, S. Brenna, F. Castelli, S. Galli, A. Maspero, A.
Sironi, Chem. Commun. (2003) 2018;
(e) F. Würthner, A. Sautter, Chem. Commun. (2000) 445.
[21] K.J. Wei, Y.S. Xie, J. Ni, M. Zhang, Q.L. Liu, Cryst. Growth Des. 6 (2006) 1341.
(c) M.H. Klingele, S. Brooker, Coord. Chem. Rev. 241 (2003) 119;
(d) Q.W. Zhai, X.Y. Wu, S.M. Chen, C.Z. Lu, W.B. Yang, Cryst. Growth Des. 6